Color photographic processing with water soluble amines and salts thereof

ABSTRACT

WHEREIN R1, R2 AND R3 REPRESENT A MEMBER SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM, AN UNSUBSTITUTED ALKYL GROUP, A SUBSTITUTED ALKYL GROUP, AN UNSUBSTITUTED ALIPHATIC GROUP, A SUBSTITUTED ALIPHATIC GROUP, AND A HETEROCYCLIC RING WITH ANOTHER GROUP, THE TOTAL NUMBER OF CARBON ATOMS IN R1,R2 AND R3 BEING LESS THAN 12.   R1-N(-R2)-R3   THE PRESENT INVENTION RELATES TO A METHOD OF PROCESSING COLOR PHOTOGRAPHIC LIGHT SENSITIVE ELEMENTS AND PARTICULARLY TO A BLEACHING PROCESS FOR COLOR PHOTOGRAPHIC LIGHT SENSITIVE ELEMENTS BY PROCESSING THEM IN A BLEACHING SOLUTION CONTAINING AT LEAST ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF AN ALIPHATIC PRIMARY AMINE, AN ALIPHATIC SECONDARY AMINE, AN ALIPHATIC TERTIARY AMINE, AND A SALT THEREOF, SAID AMINE BEING REPRESENTED BY THE GENERAL FORMULA

United States Patent Int. CL Gosc /32 US. C]. 96-60 16 Claims ABSTRACT OF THE DISCLOSURE The present invention relates to a method of processing color photographic light sensitive elements and particularly to a bleaching process for color photographic light sensitive elements by processing them in a bleaching solution containing at least one member selected from the group consisting of an aliphatic primary amine, an aliphatic secondary amine, an aliphatic tertiary amine, and a salt thereof, said amine being represented by the general formula wherein R R and R represent a member selected from the group consisting of a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aliphatic group, a substituted aliphatic group, and a heterocyclic ring with another group, the total number of carbon atoms in R R and R being less than 12.

BACKGROUND OF INVENTION In general, processings for color photographic light sensitive elements are carried out by color development, stop-fixing, bleaching (silver removal) and fixing followed by washing, hardening stabilization and the like. Various processing compositions dependent upon the types of color photographic light sensitive elements are required in these processings.

A typical example of a bleaching process for color photographic light sensitive elements is the method where by a bleaching composition containing a ferricyanide is used or a method whereby a bleaching composition containing a water-soluble iron complex salt such as Feethylenediaminetetraacetic acid complex is used. In the case of using the ferricyanide, degradation in the quality of photographic images caused by insufiicient bleaching will not tend to occur as the bleaching power of the system is sufliciently high. However, if a thiosulfate which is usually used as a fixing agent is present in the bleaching composition, the thiosulfate, will be decomposed as the oxidizing power of the ferricyanide is high. Hence there exists the drawbacks that the bleaching bath must be maintained separate from the fixing bath. Hence it requires a long period of time to accomplish the processings. Furthermore, the ferricyanide is unstable in the bleaching composition and will tend to be converted into a ferrocyanide.

On the other hand, in the case of using a bleaching composition containing a water-soluble iron complex salt such as Fe -ethylenediaminetetraacetic acid complex, a thiosulfate may be present in the system and bleaching and fixing may be carried out in a same bath. However, the bleaching power of the bleach-fixing (blixing) bath is not always suificiently high. Although various bleaching promoting agents have been investigated for improving the bleaching power in the bleaching system (e.g., German Patented May 11, 1971 Patent No. 1,127,715), there are several attendant disadvantages (i.e., color stain or color fog tends to form).

For instance, it has been known to add to the bath a thiourea or a thiourea derivative. However, in the case of adding thiourea or a thiourea derivative to the bleachfixing bath, a color stain will form when the bleach-fixing composition encounters a color developing composition.

BRIEF DESCRIPTION OF INVENTION Therefore, an object of the present invention is to provide a color photographinc bleaching process having a sutficient bleaching power with no accompanying color stains.

Another object of this invention is to provide a bleaching method for color photographic light sensitive elements using a bleach-fixing composition containing a water-soluble iron complex salt which yields no color stains.

Still another object of this invention is to provide a method of processing color photographic light sensitive elements and for providing good color images by directly subjecting the color photographic light sensitive elements to a bleach-fixing processing after color development without applying a stop-fixing processing.

As a result of various investigations, the inventors have found that the aforesaid objects of this invention can be accomplished by adding to a bleach-fixing composition an aliphatic primary amine, aliphatic secondary amine, or aliphatic tertiary amine represented by the general formula R1 N Rz wherein R R and R each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alicyclic group, or may form a heterocyclic ring together with any other group, the total sum of the carbon numbers of R R and R being less than 12, or a salt thereof. By utilizing the above-mentioned amine compound, the bleaching (silver-removing) power of the bleach-fixing bath can be markedly increased. In the case where the alkyl group or the alicyclic group is substituted, it may be substituted with a halogen, an amino group, etc.

Thus, when a photographic light sensitive element is processed in a usual bleach-fixing bath containing Fecomplex salt of ethylenediaminetetraacetic acid at a pH higher than 7, the frequently formed color stains are completely removed by incorporating the compound shown by Formula I mentioned above into the bleach-fixing bath. Moreover, a bleach promoting effect can also be obtained by incorporating the aforesaid compound in a stop-fixing bath or a bath between the stop-fixing bath and the bleachfixing bath. Further, the formation of color stains may be very effectively prevented by incorporating the aforesaid compound in a bath between the color developing bath and the stop-fixing bath, in a stop-fixing bath, or in a bath between the stop-fixing bath and the bleach-fixing bath.

When, after color development, a color photographic light sensitive element is subjected to bleach-fixing processing withing applying stopping processing or stop-fixing processing in a conventional color photographic processing, there are formed color stains which are considered to be caused by the color developer remaining after the color developing processing. Hence, in practice, a stopping or stop-fixing processing is necessary in these conventional processes. On the other hand, when the compound having the above formula is incorporated in a processing bath between the color developing and bleach-fixing or in a bleach-fixing bath, the formation of color stains is sufficiently prevented. Hence, processing by a stopping bath or a stop-fixing bath after color development is not necessary.

Now, the compounds represented by the above formula may be known as additives in the preparation of photographic emulsions for purposes other than those of the present invention, such as reduction sensitizers. However, even if the compound is added to the aforesaid processing composition in the amount used in these known techniques or if the compound is added to the photographic emulsions during the preparation thereof, neither the bleach promoting effect nor the color stain preventing elfect of the present invention can be obtained.

DETAILED DESCRIPTION OF INVENTION Typical examples of the compounds represented by the above formula used in this invention are shown below. However, it should be understood that the invention shall not be limited thereto.

The amounts of the aforesaid compound employed may range from about 03-50 g./l., particularly 2-10 g./liter of the processing bath. Since the compounds of this invention are alkaline, the pH of the bleach-fixing solution containing the compound must be adjusted to 6.4-7.1. In addition, the compounds shown above may be used alone or as mixtures thereof.

The following are typical examples of this invention showing the marked bleach promoting effects and color stain preventing effects of the compounds mentioned above. The invention shall not be limited by these examples, however.

Example 1 Each of Compounds 1-9 mentioned above was added to a bleach-fixing bath having the following composition in an amount of g. per liter of the bath.

G. Iron ethylencdiaminetetraacetate 34 Sodium carbonate (mono. hydrate) 1 varied Boric acid 45 Sodium thiosulfate 140 The additive 10 Water to make 1 liter. pH: 6.8- '-0.2.

1 The amount of the sodium carbonate was varied according to the compound of this invention to be incorporated and is shown in the following table, in which Compound 1, etc., are abbreviated as 0-1, etc.

Amount of sodium carbonate g./l. 9

4 In order to estimate the bleach promoting effect of the compounds of this invention, a control bleach-fixing bath containing no compound of this invention and having the following composition was prepared:

G. Iron ethylenediaminetetraacetate 34 Sodium carbonate (mono. hydrate) 11 Boric acid 45 Sodium thiosulfate Water to make 1 liter. pH: 6.8101.

After exposure, color development, and stop-fixing, a color photographic printing paper was processed in the bleach-fixing compositions thus prepared and the time required for the proccessing was measured, the results of which are shown in the following table.

Additive: Time (min) C-l 4 C-2 4 C-3 4 C-4 3 C-5 3 0-6 4 C-7 4 C-8 4 C-9 4 None 6 As is clear from the experimental results, it was confirmed that the addition of compounds 19 provided an excellent bleach-promoting effect. The processing temperature in this experiment was 24 C.

When color photographic light sensitive films were processed in the same manner instead of color photographic printing papers, almost identical results were obtained.

EXAMPLE 2 An aqueous solution containing 2 g./liter of each of Compounds 1-9 was prepared. After exposing, color developing and stop-fixing, a color photographic printing paper was immersed for 2 minutes in the aqueous solutions thus prepared and thereafter processed in a conventional bleach-fixing solution having the control composition of Example 1. The results were compared with the case where the same color photographic printing paper was processed in the bleach-fixing bath without being immersed in the aqueous solution containing the compound of this invention. The results are shown in the following 1 Time required for finishing the bleach-fixing processing.

As is clear from the experimental results, it was confirmed that by processing with the aqueous solution of the compound in this invention, bleaching in the subsequent bleach-fixing bath was promoted.

Also, in these experiments, color staining of the color printing paper processed by the procedures according to the invention was compared with color staining of printing paper which was processed utilizing prior art procedures. The results are shown in the following table.

2. The method of processing a color photographic light sensitive element according to claim 1 wherein said amino As is clear from these experimental results, it was conor salt thereof contained in said bath is selected from firmed that in the case of processing in the aqueous solution of this invention, the formation of color stains was remarkably reduced. The processing temperature in this experiment was 24 C.

When color photographic light sensitive films 'Were processed under the same conditions, almost identical results were obtained.

Example 3 and Additive C-1 (3- 0-3 0- -6 -7 (3-8 G- 9 Control Yellow stain 0. 18 0. 18 0. 18 0- 18 0. 18 0. 18 0- 18 0. 18 O, 18 0, 45 Magenta stain 0. 15 0. 15 0. 15 0. 15 0- 15 0 15 0. 15 0. l5 0. 16 0, Cyan stain 0. 12 O. 12 0. 12 0. 12 0- 12 0. 12 0. 12 0. 12 0, 12 0,

As is clear from these results, it was confirmed that Compounds 1-9 of this invention had very excellent stainpreventing effects. By bleach-fixing for 4 minutes in the bleach-fixing bath containing each of Compounds 1-9 used in this invention, bleaching (silver-removal) was completely accomplished, whereas it was not conducted completely in the bleach-fixing bath containing no additive. The processing temperature throughout the processings in this example was 24 C.

Almost identical results were obtained when color photographic light sensitive films were processed in the same manners.

What is claimed is:

1. In a method of color processing color photographic light sensitive elements comprising, at least, the steps of color development, stop-fixing, and bleach-fixing, the improvement which comprises processing the light sensitive element in a bath selected from the group consisting of a bleach-fixing bath and a bath located between color developing and bleach-fixing, said bath containing at least one member selected from the group consisting of water-soluble amines and salts thereof represented by the general formula:

wherein R R and R represent a member selected from the group consisting of a hydrogen atom, but no more than two of R R or R can be a hydrogen atom at any one time, an unsubstituted alkyl group, a substituted alkyl group wherein said substituent is selected from the group consisting of a halogen group and an amino group, an unsubstituted alicyclic group, a substituted alicyclic group, and a heterocyclic ring with another group, the total number of carbon atoms in R R and R being less than 12.

3. The method of processing a color photographic light sensitive element according to claim 1 wherein the amount of said amine or said thereof to be incorporated in said bath is 03-50 g. per one liter of said bath.

4. In a method of color processing a photographic light sensitive color element comprising image-wise exposing the element, developing the exposed element by a developer capable of forming a silver and a color image and bleach-fixing the developed element to remove the silver image, the improvement which comprises processing the color element in a bleach-fixing bath containing a watersoluble iron complex salt and a water soluble amine compound selected from the group consisting of 5. The process of claim 4 wherein said water-soluble iron complex salt is the iron complex salt of ethylene diamine tetra-acetic acid.

6. The method of processing a color photographic light sensitive element according to claim 4 wherein the amount of said amine or salt thereof to be incorporated in said bath is 0.3-5 0 g. per one liter of said bath.

7. In a method of color processing a photographic light sensitive color element comprising image-wise exposing the element, developing the exposed element by a de- 8. The process of claim 7 wherein said water-soluble iron complex salt is the iron complex salt of ethylene diamine tetra-acetic acid.

9. The method of processing a color photographic light sensitive element according to claim 7 wherein the amount of said compound to be incorporated in said bath is 0.3- g. per one liter of said bath.

10. The process of claim 1 wherein said amine salt is an acid halide salt.

11. The process of claim 4 wherein said amine salt is an acid halide salt.

12. The process of claim 7 wherein said amine salt is an acid halide salt.

13. The process of claim 1 wherein the substituted alicyclic group is substituted with a halogen or an amino group.

14. The process of claim 1 wherein bleach-fixing is conducted at a pH of at least about 7.

15. The process of claim 4 wherein bleach-fixing is conducted at a pH of at least about 7.

16. The process of claim 7 wherein bleach-fixing is conducted at a pH of at least about 7.

References Cited UNITED STATES PATENTS 3,293,036 10/ 1967 Meckl et a1 96-60 FOREIGN PATENTS 774,545 5/1957 Great Britain 9660BF 933,008 5/ 1963 Great Britain 9660BF NORMAN G. TORCHIN, Primary Examiner J. L. GOODROW, Assistant Examiner U.S. c1. X.R. 96-60BF, 61 

